EP0152915A2 - Produits de digestion de polyalkylène téréphtalate polymères, et de polyols contenant un acide polycarboxylique et mousses polymères obtenus à partir de ceux-ci - Google Patents

Produits de digestion de polyalkylène téréphtalate polymères, et de polyols contenant un acide polycarboxylique et mousses polymères obtenus à partir de ceux-ci Download PDF

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Publication number
EP0152915A2
EP0152915A2 EP19850101596 EP85101596A EP0152915A2 EP 0152915 A2 EP0152915 A2 EP 0152915A2 EP 19850101596 EP19850101596 EP 19850101596 EP 85101596 A EP85101596 A EP 85101596A EP 0152915 A2 EP0152915 A2 EP 0152915A2
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Prior art keywords
digesting
polyol
polycarboxylic acid
acid component
mixture
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Ceased
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EP19850101596
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German (de)
English (en)
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EP0152915A3 (fr
Inventor
Richard K. Hallmark
Michael J. Skowronski
William D. Stephens
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Celotex Corp
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Walter Jim Resources Inc
Celotex Corp
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Publication of EP0152915A2 publication Critical patent/EP0152915A2/fr
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J11/00—Recovery or working-up of waste materials
    • C08J11/04—Recovery or working-up of waste materials of polymers
    • C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
    • C08J11/18—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material
    • C08J11/22—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material by treatment with organic oxygen-containing compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B11/00—Layered products comprising a layer of bituminous or tarry substances
    • B32B11/04—Layered products comprising a layer of bituminous or tarry substances comprising such bituminous or tarry substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B11/048—Layered products comprising a layer of bituminous or tarry substances comprising such bituminous or tarry substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material of foam
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/046—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of foam
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B29/00—Layered products comprising a layer of paper or cardboard
    • B32B29/002—Layered products comprising a layer of paper or cardboard as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B29/007—Layered products comprising a layer of paper or cardboard as the main or only constituent of a layer, which is next to another layer of the same or of a different material next to a foam layer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
    • C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups
    • C08G18/4211—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols
    • C08G18/4213—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols from terephthalic acid and dialcohols
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/10—Inorganic fibres
    • B32B2262/101—Glass fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2266/00—Composition of foam
    • B32B2266/02—Organic
    • B32B2266/0214—Materials belonging to B32B27/00
    • B32B2266/0278—Polyurethane
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2115/00—Oligomerisation
    • C08G2115/02—Oligomerisation to isocyanurate groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2170/00—Compositions for adhesives
    • C08G2170/60—Compositions for foaming; Foamed or intumescent adhesives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/62—Plastics recycling; Rubber recycling
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]

Definitions

  • polyester polyols which are the hydroxyl-terminated digestion products of (a) polyalkylene terephthalate polymers and (b) polycarboxylic acid-containing polyols.
  • the polyols are useful in the preparation of cellular foam materials, particularly polyisocyanurate and polyurethane foams.
  • foams characterized by isocyanurate and urethane linkages are well known in the art. Generally, these foams are prepared by reacting an organic polyisocyanate with a polyol in the presence of a blowing agent and a catalyst(s). Polyester polyols of many types can be used as the polyol components in the production of these foams.
  • U. S. Patent No. 4,039,487 discloses the use of aromatic polyester polyols to prepare polyisocyanurate foams. Although the foams of this patent have good fire resistance and low smoke evolution upon combustion, they have a relatively high friability. Furthermore, the polyols are comparatively expensive to manufacture.
  • U. S. Patent No. 4,092,276 also discloses the use of rather costly aromatic polyester polyols in preparing polyisocyanurate foams. Another disadvantage of these foams is that they do not have especially high compressive strength. A further problem with using aromatic polyester polyols, particularly those of low molecular weight, is that the polyols tend to be solid at room temperature, or to be characterized by very high viscosity and poor solubility in resin mixtures, thus making them difficult to handle.
  • polyester wastes Another source of aromatic polyester polyols is available through the recovery of polyester wastes.
  • High molecular weight polyesters of terephthalic acid and aliphatic dihydric alcohols are well known in the art. These high molecular weight polyesters, especially polyethylene terephthalate (PET), are used commercially for the manufacture of packaging film, fibers, electrical insulators, molded articles, such as PET beverage bottles, etc.
  • PET polyethylene terephthalate
  • the various manufacturing processes unfortunately generate considerable waste as the polyester is processed into commercial form. Also, the tremendous quantities of spent consumer goods containing the polyester constitute a huge supply of scrap polyester material.
  • U. S. Patent No. 4,223,068 discloses the manufacture of rigid polyurethane foam wherein 5 to 30 percent of the weight of the organic polyol used in the manufacture is a digestion product of polyalkylene terephthalate residues or scraps digested with organic polyols.
  • the preparation of isocyanurate modified polyurethane foams utilizing a digestion product of polyalkylene terephthalate scrap dissolved in one or more organic polyols is described in U . S . Patent No. 4,417,001. While these foams are characterized by desirable physical properties, deficiencies have been encountered in the fluidity and storage stability of polyol digestion products disclosed for use in preparing the foams. These deficiencies lead to inefficiency in the foam production.
  • the present invention concerns a storage stable polyol composition for use in preparing polymeric foam materials, particularly polyurethane and polyisocyanurate foams, of reduced friability and high thermal stability and compressive strength, and a method of producing the polyol composition.
  • the present invention also is directed to improved cellular foams, especially polyisocyanurate and polyurethane foams, having a combination of advantageous properties, including a reduced friability and high thermal stability and compressive strength, and an improved method of producing the foams.
  • the present invention also concerns an improved polyisocyanurate foam material characterized by a high degree of fire resistance with low smoke evolution and flame spread on combustion, and the formation of a protective char over unburnt foam upon combustion.
  • the present invention is concerned with polyisocyanurate foams which are characterized by a high conversion to trimer.
  • the present invention also involves closed cell polyisocyanurate and polyurethane foam materials which can be used in building panels which are highly insulating, thermally resistant, low in friability, soundproof and self-supporting.
  • an improved polyester polyol which is prepared by digesting polyalkylene terephthalate polymers with a polycarboxylic acid component-containing polyol, the polycarboxylic acid component having ring units with two groups on adjacent or alternate ring positions, the ring unit content of the polycarboxylic acid component being sufficient for improved storage stability of the digestion product.
  • the invention particularly relates to a polyester polyol mixture comprising the reaction product obtained by digesting polyalkylene terephthalate with a digesting medium comprising a polycarboxylic acid component-containing polyol derived from a digesting polycarboxylic acid component and a digesting polyol component, wherein the digesting polycarboxylic acid component has ring units with two groups on adjacent or alternate ring positions, the ring unit content of the digesting polycarboxylic acid component being sufficient for improved storage stability of the digestion product.
  • a preferred digesting polyol of the invention contains o-phthalic, isophthalic and/or trimellitic acid residues.
  • o-phthalic, isophthalic and trimellitic acid residues are meant the groups respectively.
  • the polyalkylene terephthalate digestion products can be reacted with organic polyisocyanates in the presence of a blowing agent and catalyst to produce polyisocyanurate and polyurethane foams, and laminates thereof.
  • the process of producing the foam benefits considerably from the fluidity and improved storage stability of the digestion products of the invention.
  • the polyalkylene terephthalate (principally polyethylene terephthalate) polymers to be digested are available in the form of films, fibers, and shaped articles.
  • polyalkylene terephthalate polymers are available as sludges which are obtained as cleanup by-products from polyalkylene terephthalate manufacturing plants.
  • the waste or scrap polyalkylene terephthalate contains recurring units of the formula wherein G represents a divalent organic radical containing from 2 to 10 carbon atoms attached to the adjacent oxygen atoms by saturated carbon atoms.
  • G represents a divalent organic radical containing from 2 to 10 carbon atoms attached to the adjacent oxygen atoms by saturated carbon atoms.
  • G is -C 2 H 4 -.
  • the molecular weight of such polyalkylene terephthalate polymers is at least about 15,000 and ranges upward to 100,000 or more. Lower molecular weight oligomers of the polyalkylene terephthalates also can be used.
  • the polyalkylene terephthalate polymers are digested or degraded with a digesting medium comprising a polycarboxylic acid component-containing polyol.
  • the digesting medium may comprise a polyol and a polycarboxylic acid or acid derivative, such as an anhydride or ester of the polycarboxylic acid.
  • the ingredients can be introduced in various ways in the digesting process. For example, all ingredients can be charged at the same time to the reacting vessel and thereupon reacted together.
  • the polyalkylene terephthalate first is reacted with a polyol, and the polycarboxylic acid or acid derivative thereof subsequently is added to the reactor and the reaction continued to completion.
  • mixtures of digesting reactants such as mixtures of diols, like diethylene or dipropylene glycol, and polyester polyols, like reaction products of mixtures of phthalic anhydride and said diols, can be introduced together to the reactor.
  • the polyols of the digesting medium desirably are low molecular weight polyols which can be aliphatic, cycloaliphatic, aromatic, araliphatic and/or heterocyclic, and are preferably selected from the group consisting of diols and triols.
  • alkoxylated triols are employed.
  • the polyol is an aliphatic dihydric alcohol which desirably has from 2 to 16 carbon atoms.
  • the molecular weight of the digesting polyol advantageously ranges from about 60 to about 500.
  • suitable diols include alkylene glycols and glycol ethers, such as ethylene, oxydiethylene, propylene, oxydipropylene, butylene, pentylene, hexylene, and octamethylene glycols, and isomeric forms thereof, and the polyoxyalkylene glycols such as polyoxyethylene and polyoxypropylene glycols, 1,4-bis-hydroxymethyl cyclohexane, dimethylol dicyclopentadiene, 1,3-cyclohexanediol, 1,4-cyclohexanediol, and in general hydroxy-terminated ethers or mixed ether esters having a molecular weight of about 500 or less.
  • alkylene glycols and glycol ethers such as ethylene, oxydiethylene, propylene, oxydipropylene, butylene, pentylene, hexylene, and octamethylene glycols, and isomeric forms thereof
  • the digesting polyols may, of course, be used as mixtures of two or more polyols.
  • the polyols may include substituents which are inert in the digestion reaction, for example, chlorine and bromine substituents.
  • Preferred polyols are polyoxyethylene glycols, diethylene glycol and dipropylene glycol, with the latter two glycols being especially suitable.
  • the digesting medium must contain a polycarboxylic acid or acids, or derivatives thereof, having an effective amount of the above-described ring residues for storage stability improvement of the resulting digestion product.
  • the acid compounds containing the ring residues may be aromatic, cycloaliphatic, araliphatic and/or heterocyclic compounds, and preferably are aromatic.
  • the acid compounds may have additional - - groups or -OH groups, and further may include substituents which are inert in the digestion reaction, for example, chlorine and bromine substituents.
  • Polycarboxylic acids or acid derivatives introduced in the digestion or depolymerization will be converted to esters during the process.
  • the acids or acid derivatives can be pre-reacted to form esters and these esters then introduced in the depolymerization.
  • ring residue-containing acid compounds are phthalic anhydride, isophthalic acid, trimellitic anhydride, tetrahydrophthalic anhydride, tetrachlorophthalic anhydride, tetrabromophthalic anhydride, 1,4,5,6,7,7-hexa- chloro-5-norbornene-2,3-dicarboxylic anhydride, and 1,8-naphthalic anhydride.
  • other polybasic-carboxylic acid components may be used in the depolymerization.
  • the optional polybasic-carboxylic acids may be aliphatic, cycloaliphatic, aromatic, araliphatic and/or heterocyclic and may be substituted, for example, with halogen atoms and/or may be unsaturated.
  • the digestion of the polyalkylene terephthalate polymer is conveniently carried out under normal depolymerization conditions well known and described in the prior art.
  • the digestion or depolymerization can be conducted in the absence of a liquid reaction medium composed of material other than the digesting ingredients.
  • the reaction suitably is performed under a flow of nitrogen and at atmospheric pressure and temperatures from about 150° C. to about 250° C. for a period from about one hour to about ten hours.
  • the digestion reaction can be carried out as a batch process or continuously, and is normally catalyzed.
  • enough depolymerization or transesterification catalyst is added to the reaction mixture to suitably promote the reaction. Any conventional transesterification catalyst (single compound or mixture of compounds) can be used.
  • the depolymerization may be initiated by reacting the polyalkylene terephthalate material (e.g., polyethylene terephthalate) with a polyol, such as diethylene and/or dipropylene glycol, in the presence of a catalyst, such as tetrabutyl titanate, until a solution of the polyalkylene terephthalate is obtained. Then the acid component, such as phthalic anhydride, or an ester thereof, such as the product of a catalyzed esterification reaction between phthalic anhydride and diethylene and/or dipropylene glycol, is added and the depolymerization is completed.
  • a catalyst such as tetrabutyl titanate
  • proportions of polyalkylene terephthalate to polyol to acid or derivative thereof may be varied to a considerable degree in accordance with the product desired. At all events, sufficient polyol and acid component should be used to form a polyester polyol having long-term storage stability and capable of efficiently polymerizing with organic polyisocyanates in the formation of rigid foams.
  • the depolymerization of polyethylene terephthalate is accomplished by digesting the polymer with the digesting polyol, preferably diethylene glycol (DEG), and the polycarboxylic acid component, preferably phthalic anhydride (PA).
  • the digesting polyol preferably diethylene glycol (DEG)
  • the polycarboxylic acid component preferably phthalic anhydride (PA).
  • suitable molar proportions of reactants may be as follows:
  • the enhanced storage stability of the polyol digestion product is attributable to the presence of the ring unit-containing polycarboxylic acid component in the digesting medium, much lower PET:polycarboxylic acid component mole ratios, with an accompanying increase, if desired, in the amount of digesting polyol to maintain the equivalent weight, may of course be employed.
  • the cost of the digestion product increases with increasing content of the stabilizing acid component.
  • the molar proportions are as follows:
  • the digestion process is considered to be substantially complete when a solution of the sample being digested is formed.
  • some polyalkylene terephthalate materials contain dispersed solids which can be catalyst particles (left over from the processing by which the terephthalate was produced); or may be pigments or other foreign substances. Such dispersed solids may remain in the digestion product, so long as they are substantially inert in the subsequent preparation of rigid polymeric foam.
  • digested polyol mixture of the invention generally can be employed without being filtered, it is also possible to filter this mixture prior to its subsequent utilization in foam preparations.
  • the properties of the digested polyol mixtures of the present invention fall within rather broad ranges because of the variable nature of the polyalkylene terephthalate materials themselves. Accordingly, the viscosities (Brookfield) of the digested polyol mixtures measured in cps. at 25° C. fall within a rather broad range from about 500 to about 50,000, preferably about 500 to about 20,000, and most preferably about 700 to about 12,000; the hydroxyl number values fall within a range of from about 700 to about 120, preferably about 250 to about 600, and most preferably from about 300 to about 475; the acid number falls within a range of from about .2 to about 20 and preferably about .2 to about 10.
  • a most preferred digested polyol mixture of the invention is characterized by a viscosity in cps. at 25° C. of about 700 to about 12,000, a free diethylene glycol content of from about 8 to about 30 percent by weight of said mixture, a free ethylene glycol content of from about 2 to about 8 percent by weight of said mixture, a hydroxyl number within a range of from about 300 to about 475, and an acid number of about .2 to about 10.
  • the polyol mixtures of the present invention may be used in the preparation of both cellular and non-cellular polymers.
  • the latter polymers such as the polyisocyanurates and polyurethanes, can be prepared by using standard techniques known to those skilled in the art.
  • the polyol mixtures are particularly useful in the preparation of polyisocyanurate foams and polyurethane foams. These foams can be prepared by mixing together the organic polyisocyanate with the polyol, catalyst and blowing agent at temperatures ranging from about 0° C. to 150° C.
  • the polyurethane foams can be prepared by reacting the polyol mixture of the invention and polyisocyanate on an essentially 1:1 to 1:1.2 equivalent basis.
  • the polyol mixture of the invention is employed in admixture with at least one other polyol to produce polyurethane foams.
  • the polyol mixture of the invention can comprise about 5 to 100, preferably about 20 to 50, weight percent of the total polyol content in the foam preparations.
  • the polyisocyanurate foams of the invention are prepared by reacting the polyisocyanate with a minor amount of polyol, wherein the polyol digestion mixture comprises about 5 to 100 weight percent of the total polyol content in the foam preparations.
  • any organic polyisocyanate can be employed in the preparation of the foams of the present invention.
  • the organic polyisocyanates which can be used include aromatic, aliphatic and cycloaliphatic polyisocyanates and combinations thereof.
  • diisocyanates such as m-phenylene diisocyanate, toluene-2, 4-diisocyanate, toluene-2,6-diisocyanate, mixtures of 2,4- and 2,6-toluene diisocyanate, hexamethylene-1,6-diisocyanate, tetramethylene-1, 4-diisocyanate, cyclohexane-1,4-diisocyanate, hexahydrotoluene 2,4- and 2,6-diisocyanate, naphthalene-1,5-diisocyanate, diphenylmethane-4,4'-diisocyanate, 4,4'-diphenylenediisocyanate, 3,3'-di- methoxy-4,4'-biphenyldiisocyanate, 3,3'-dimethyl-4, 4'-biphenyldiisocyanate, and
  • the polyols which can be employed in combination with the polyol mixture of the invention in the preparation of the polyurethane and polyisocyanurate foam compositions include, for example, monomeric polyols, such as ethylene glycol, the oxyalkylene adducts of polyol bases wherein the oxyalkylene portion is derived from a monomeric unit such as ethylene oxide, propylene oxide, butylene oxide and mixtures thereof.
  • the polyol initiators include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butanediol, 1,4-butanediol, hexanetriol, glycerol, trimethylolpropane, triethylolpropane, pentaerythritol, sorbitol, sucrose, toluene diamine and bisphenol A, polyethers such as polyethylene ether glycols, polypropylene ether glycols, polytetramethylene ether glycols, and alkylene oxide adducts of polyhydric alcohols including those listed above; hydroxy terminated tertiary amines of the formula: wherein R is an alkylene radical containing at least 2 to 6 carbon atoms and E is a polyoxyalkylene chain; amine based polyethers of the formula: wherein E is a polyoxyalkylene chain and Y is selected from the group consisting of alkyl
  • Typical polyether polyols include polyoxyethylene glycol, polyoxypropylene glycol, polyoxybutylene glycol, polytetramethylene glycol, block copolymers, for example, combinations of polyoxypropylene and polyoxyethylene glycols, poly-1,2-oxybutylene and polyoxyethylene glycols, and poly-1,4-oxybutylene and polyoxyethylene glycols, and random copolymer glycols prepared from blends or sequential addition of two or more alkylene oxides.
  • the polyether polyols which can be employed in the present invention include oxyalkylene polymers which have an oxygen/carbon ratio from about 1:2 to 1:4 and preferably an oxygen carbon atom ratio from about 1:2.8 to 1:4 and from about 2 to 6 terminal hydroxyl groups, preferably about 2 to 4 terminal hydroxyl groups.
  • the polyether polyols generally have an average equivalent weight from about 80 to 10,000 and preferably have an average equivalent weight from about 100 to about 6000.
  • Polyoxypropylene glycols having molecular weights from about 200 to about 4000 corresponding to equivalent weights from about 100 to 2000 and mixtures thereof are particularly useful as polyol reactants.
  • Polyol blends such as a mixture of high molecular weight polyether polyols with lower molecular weight polyether polyols or monomeric polyols can also be employed.
  • Any suitable hydroxy terminated polyester may also be used in combination with the polyol mixture of the invention. These can be obtained from the reaction of polycarboxylic acids and polyhydric alcohols.
  • suitable polycarboxylic acids may be oxalic acid, ma- lonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, basillic acid, thapsic acid, maleic acid, fumaric acid, glutaconic acid, isophthalic acid and terephthalic acid.
  • Suitable polyhydric alcohols include the following: ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, 1,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-hexanediol, glycerol, trimethylolpropane, trimethylolethane, hexane 1,2,6-triol, a-methylglucoside, pentaerythritol, sorbitol, sucrose, and compounds derived from phenols such as 2,2-bis(4-hydroxyphenol) propane.
  • graft polyols are prepared by the in situ polymerization product of a vinyl monomer in a reactive polyol medium and in the presence of a free radical initiator. The reaction is generally carried out at a temperature ranging from about 40° C. to 150°C.
  • blowing agent typically employed in similar prior art foam products containing polyisocyanurate and/or polyurethane linkages can be employed in the foam compositions of the present invention.
  • these blowing agents are liquids having a boiling point between minus 50° C. and plus 100° C. and preferably between 0° C. and 50° C.
  • the preferred liquids are hydrocarbons or halohydrocarbons.
  • suitable blowing agents include, among others, chlorinated and fluorinated hydrocarbons such as trichlorofluoromethane, CCl 2 FCClF 2 , CC1 2 FCF 3 , diethylether, isopropyl ether, n-pentane, cyclopentane, and 2-methylbutane.
  • Trichlorofluoromethane is a preferred blowing agent.
  • the blowing agents are employed in an amount sufficient to give the resultant foam the desired bulk density which is generally between 0.5 and 10, and preferably between 1 and 5 pounds per cubic foot (between 8 and 160, and preferably between 16 and 40 kg/m 3 ).
  • the blowing agent generally comprises from 1 to 30, and preferably comprises from 5 to 20 weight percent of the composition.
  • the blowing agent has a boiling point at or below ambient, it is maintained under pressure until mixed with the other components. Alternatively, it can be maintained at subambient temperatures until mixed with the other components.
  • any suitable surfactant can be employed in the foams of this invention.
  • Successful results have been obtained with silicone/ethylene oxide/propylene oxide copolymers as surfactants.
  • surfactants useful in the present invention include, among others, polydimethylsiloxane-polyoxyalkylene block copolymers available from the Union Carbide Corporation under the trade names "L-5420" and “L-5340” and from the Dow Corning Corporation under the trade name "DC-193".
  • Other suitable surfactants are those described in U.S. Pat. No. 4,365,024 and European patent application No. 84104783.0.
  • the surfactant comprises from about 0.05 to 10, and preferably from 0.1 to 6, weight percent of the foam-forming composition.
  • any of the catalysts conventionally employed in the art to catalyze the reaction of an isocyanate with a reactive hydrogen containing compound can be employed in the foam preparations of the invention.
  • Such catalysts include organic and inorganic acid salts of, and organometallic derivatives of, bismuth, lead, tin, iron, antimony, uranium, cadmium, cobalt, thorium, aluminum, mercury, zinc, nickel, cerium, molybdenum, vanadium, copper, manganese, and zirconium, as well as phosphines and tertiary organic amines.
  • catalysts examples include dibutyltin dilaurate, dibutyltin diacetate, stannous octoate, lead octoate, cobalt naphthenate, triethylamine, triethylenediamine, N,N,N',N'-tetramethylethylenediamine, 1,1, 3,3-tetramethylguanidine, N,N,N',N'-tetramethyl-1,3-butanediamine, N,N-dimethylethanolamine, N,N-diethylethanolamine, and the like.
  • the catalysts generally comprise from 0.1 to 20, and preferably from 0.3 to 10, weight percent of the total composition.
  • additives may also be included in the foam formulations. Included are flame retardants, such as tris(2-chloroethyl)-phosphate, dispersing agents, plasticizers, fillers and pigments.
  • the organic polyisocyanate is polymethylene polyphenylisocyanate.
  • the polymethylene polyphenylisocyanates desirably have a functionality of at least 2.1 and preferably 2.5 to 3.2. These preferred polymethylene polyphenylisocyanates generally have an equivalent weight between 120 and 180 and preferably have an equivalent weight between 130 and 145.
  • the friability of foams made with these polyisocyanates is desirably less than 30%, preferably less than 20%.
  • a preferred subclass of polymethylene polyphenyliso cyanates especially useful in the present invention is a mixture of those of the following formula: wherein n is an integer from 0 to 8 and wherein the mixture has the above-described functionality and equivalent weight.
  • This mixture should have a viscosity between 100 and 4,000 and preferably 250 to 2500 centipoises measured at 25° C. in order to be practical for use in the present invention.
  • Suitable polymethylene polyphenylisocyanates useful in the present invention include those of the above formula, wherein n is 1 as well as mixtures wherein n can have any value from 0 to 8 as long as the mixture has the specified equivalent weight.
  • the preferred polymethylene polyphenyl isocyanates are described in British Patent Specification No. 1,433,641.
  • the synthesis of polymethylene polyphenylisocyanates is described in Seeger et al., U. S. Pat. No. 2,683,730 and in Powers U.S. Pat. No. 3,526,652 at column 3, lines 6-21.
  • the polymethylene polyphenylisocyanate and the polyol are generally mixed in an equivalent ratio of 1.5:1 to 6:1 and preferably 2:1 to 5:1. In ranges outside these proportions the reaction yields a product having undesirable physical characteristics. At higher ratios the product has an undesirably high friability. At lower ratios the product has an undesirably high flammability.
  • any catalysts known to catalyze the trimerization of isocyanates to form isocyanurates, and to catalyze the reaction of isocyanate groups with hydroxyl groups to form polyurethanes can be employed.
  • the preferred catalysts give cream times of 15 to 30 seconds and firm times of 25 to 80 seconds.
  • One preferred type of catalyst is a mixture of a tertiary amino phenol, such as 2,4,6- tris(dimethylaminomethyl)phenol, and an alkali metal carboxylate, such as potassium-2-ethyl hexoate, the synthesis and use of which are described in U.S. Patent No. 4,169,921.
  • the equivalent ratio of tertiary amino phenol to alkali metal carboxylate in the cocatalyst composition is desirably about .4:1 to 2.5:1.
  • Another catalyst system is that employing an epoxide, an N-substituted aziridine, and a tertiary amine. The synthesis and use of such a catalyst are described in U. S. Pat. No. 3,799,896.
  • the catalysts generally comprise from 0.1 to 20 and preferably from 0.3 to 10 weight percent of the total composition.
  • the apparatus 10 comprises an isocyanate tank 11, a polyol tank 12, and a catalyst tank 13, each respectively connected to outlet lines 14, 15, and 16.
  • the lines 14, 15, and 16 form the inlet to metering pumps 17, 18, and 19.
  • the pumps 17, 18, and 19 discharge respectively through lines 20, 21, and 22 which are in turn respectively connected to flexible lines 23, 24, and 25.
  • the flexible lines 23, 24, and 25 discharge to mixing head 29.
  • the apparatus 10 is also provided with a roll 30 of lower substrate material and a roll 31 of upper substrate material.
  • the apparatus 10 is also provided with metering rolls 32 and 33, and an oven 35 provided with vents 36, 36' for blowing hot air.
  • the apparatus 10 is also provided with pull rolls 38, 39 and cutting knife 44.
  • the isocyanate tank 11 is charged with the organic polyisocyanate admixed with the blowing agent and the surfactant
  • the polyol tank 12 is charged with the polyol mixture of the invention
  • the catalyst tank 13 is charged with the catalyst composition.
  • the speeds of the pumps 17, 18, and 19 are adjusted to give the desired ratios of the ingredients in the tanks 11, 12, and 13.
  • These ingredients pass respectively through lines 20, 21, and 22 as well as lines 23, 24, and 25, whereupon they are mixed in the mixing head 29 and discharged therefrom.
  • lines 21 and 22 can be combined prior to the mixing head.
  • the pull rolls 38, 39 each of which has a flexible outer sheath 40, 41 are caused to rotate in the direction of the arrows by a power source (not shown).
  • a power source not shown
  • lower substrate material is pulled from the roll 30, whereas upper substrate material is pulled from the roll 31.
  • the substrate material passes over idler rollers such as idler rollers 46 and 47 and is directed to the nip between metering rolls 32, 33.
  • the mixing head 29 is caused to move back and forth, i.e. out of the plane of the paper by virtue of its mounting on reversible mechanism 49. In this manner, an even amount of material can be maintained upstream of the nip between the metering rolls 32, 33.
  • the temperature within the oven is controlled by varying the temperature of the hot air from vents 36, 36', in order to insure that the temperature within the oven 35 is maintained within the herein described limits.
  • the composite structure 55 then leaves the oven 35, passes between the nip of the pull rolls 38, 39 and is cut by knife 44 into individual panels 57, 57'.
  • the tanks 11, 12, and 13 can be provided with refrigeration means in order to maintain the reactants at subambient temperatures.
  • FIG. 2 of the drawings there is shown a laminated building panel 60 of the invention.
  • the building panel 60 comprises a single facing sheet 61 having thereon a cellular material 62 of the present invention.
  • Figure 3 shows a building panel 70 having two facing sheets 71 and 72 on either side of a cellular material 73.
  • Any facing sheet previously employed to produce building panels can be employed in the present invention.
  • suitable facing sheets include, among others, those of kraft paper, aluminum, and asphalt impregnated felts, as well as laminates of two or more of the above.
  • the foam materials of the invention can also be used, with or without a facer(s), for pipe insulation.
  • the foam materials of the invention can contain various reinforcement materials, such as a quantity of glass fibers, as described in U. S. Patent Nos. 4,118,533 and 4,284,683.
  • This example illustrates the preparation of a digested polyol mixture of the present invention.
  • the resultant polyol mixture had an acid number of 1.4, a viscosity of 1250 cps at 25°C., a free diethylene glycol content of 19.06%, a free ethylene glycol content of 3.66%, and a hydroxyl number of 439.5.
  • This example illustrates the synthesis of a rigid polyisocyanurate foam utilizing the digested polyol mixture of Example 1.
  • the foam was prepared using a Hennecke foam metering and dispensing machine. Items A, B and C were premixed together, metered and injected into one side of the high pressure impingement mixing chamber of the machine. Items E, F and G were premixed together in a container. 7.8 parts of this catalyst mixture, and a metered amount of item D were injected into the other side of the high pressure impingement mixing chamber. After mixing, all ingredients were dispensed into an appropriate container, yielding a polyisocyanurate foam.
  • Item A is a polymethylene polyphenyl isocyanate having an equivalent weight of 138, an acidity of 0.03% HC1, and a viscosity of 2000 centipoises at 25°C. and is available from the Mobay Chemical Company, Pittsburgh, Pa. under the trade name MONDUR MR-200.
  • Item C is the surfactant supplied by Jim Walter Resources, Inc. under the trade name Foamstab 100.
  • Item E is that supplied by the Rohm & Haas Chemical Company under the trade name DMP-30.
  • Item F is employed in the form of a 70 weight % solution in the polyoxyethylene glycol (Item G) sold by the Union Carbide Corporation under the trade name Carbowax 200.
  • the catalyst mixture of Items E, F and G added in the above-described foam preparation is a blend of DMP-30: potassium-2-ethyl hexoate: polyoxyethylene glycol in a 0.84:2.50:6.66 weight ratio.
  • This example illustrates the digestion of 4 in. (0.64 cm) ground polyethylene terephthalate bottle scrap to produce a digested polyol mixture of the present invention.
  • the resulting liquid product was poured through a 297 micron screen and vacuum filtered to remove fine particles therefrom.
  • the polyol mixture had a hydroxyl number of 460.
  • This example illustrates the synthesis of a rigid polyurethane foam utilizing the digested polyol mixture of Example 3.
  • the foam was prepared using a Martin-Sweets Machine.
  • a large batch of polyol premix was prepared by mixing together Items B, C, D, E, F and G, and cooling the resulting mixture to 15°C.
  • 156.0 parts of Item A at a temperature of 15°C were charged to the mixing chamber of the Martin-Sweets Machine.
  • 164.0 parts of the polyol premix at a temperature of 15° C. were charged to the mixing chamber, along with 0.7 part of Item H.
  • the ingredients were mixed at 5000 rpm, and thereafter deposited into a box to yield a rigid polyurethane foam.
  • Item A is a polymethylene polyphenyl isocyanate having a viscosity of 150-250 centipoises at 25°C and is available from the Mobay Chemical Corporation, Pittsburgh, Pa. under the trade name Mondur MR.
  • Item B is that supplied by the Olin Corporation under the trade name Poly G-71-530.
  • Item D is that supplied by the Stauffer Chemical Corporation under the trade name Fyrol 6.
  • Item F is the surfactant supplied by Jim Walter Resources, Inc. under the trade name Foamstab 110.
  • Item G is that supplied by Abbott Laboratories under the trade name Polycat 8.
  • Item H is that supplied by Cincinnati Milacron under the trade name Advastab TM 181.

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
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EP19850101596 1984-02-22 1985-02-14 Produits de digestion de polyalkylène téréphtalate polymères, et de polyols contenant un acide polycarboxylique et mousses polymères obtenus à partir de ceux-ci Ceased EP0152915A3 (fr)

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TWI819147B (zh) * 2018-11-28 2023-10-21 日商Ｄｉｃ股份有限公司 反應性接著劑及其製造方法、積層體及包裝體
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US4539341A (en) 1985-09-03
ES540596A0 (es) 1986-06-01
ES8608013A1 (es) 1986-06-01
AU3809285A (en) 1985-08-29
CA1261983A (fr) 1989-09-26
NO850392L (no) 1985-08-23
ES8705497A1 (es) 1987-05-01
ZA85805B (en) 1986-04-30
EP0152915A3 (fr) 1987-05-06
JPS60210626A (ja) 1985-10-23
ES550730A0 (es) 1987-05-01
DK79885A (da) 1985-08-23
CA1294734C (fr) 1992-01-21
DK79885D0 (da) 1985-02-21

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